EP0275771A1 - Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters - Google Patents

Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters Download PDF

Info

Publication number
EP0275771A1
EP0275771A1 EP87402923A EP87402923A EP0275771A1 EP 0275771 A1 EP0275771 A1 EP 0275771A1 EP 87402923 A EP87402923 A EP 87402923A EP 87402923 A EP87402923 A EP 87402923A EP 0275771 A1 EP0275771 A1 EP 0275771A1
Authority
EP
European Patent Office
Prior art keywords
acid
moles
hydrogen peroxide
ester
iodide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87402923A
Other languages
German (de)
French (fr)
Other versions
EP0275771B1 (en
Inventor
André Lantz
Pascal Michaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT87402923T priority Critical patent/ATE45346T1/en
Publication of EP0275771A1 publication Critical patent/EP0275771A1/en
Application granted granted Critical
Publication of EP0275771B1 publication Critical patent/EP0275771B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/38—Halogenated alcohols containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/40—Halogenated alcohols perhalogenated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
    • C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids

Definitions

  • the present invention relates to the synthesis of tetrahydro-1,1,2,2 perfluoroalkanols (R F CH2CH2OH) and their esters by oxidation of the corresponding 2-perfluoroalkylethyl iodides (R F CH2CH2I) using hydrogen peroxide.
  • the perfluoroalkyl radical R F can contain from 1 to 20 carbon atoms and can be straight or branched chain.
  • polyfluorinated alcohols and esters are useful intermediates for the manufacture of surfactants and hydrophobic and oleophobic products. They can in particular be easily transformed into acrylic or methacrylic esters, the polymerization of which, optionally with other monomers, provides hydrophobic and oleophobic finishing agents for textiles, leather, paper or other substrates. The mixtures of alcohols and esters can also be entirely transformed into alcohols.
  • esters R F CH2CH2OCOR by reaction of an iodide R F CH2CH2I with a carboxylic acid salt RCOOH.
  • the alcohols R F CH2CH2OH can also be obtained according to the process of patent FR 2 096 179 which consists in preparing the nitrates R F CH2CH2ONO2 by reaction of the iodides R F CH2CH2I with nitric acid and in hydrogenating these nitrates into alcohol.
  • this process has the drawback of requiring two reaction stages, the last of which must be carried out under high hydrogen pressure.
  • Patent FR 2 180 113 describes a process for manufacturing mixtures of alcohols R F CH2CH2OH and formates R F CH2CH2OCOH by reaction at high temperature of iodides R F CH2CH2I with dimethylformamide in the presence of a little water.
  • good selectivity for alcohol and formate can only be obtained by using very large amounts of dimethylformamide.
  • the process according to the invention which consists in oxidizing a 2-perfluoroalkylethyl iodide by means of hydrogen peroxide within a carboxylic acid or an ester of such an acid and in the presence of sulfuric acid is characterized in that, for one mole of 2-perfluoroalkylethyl iodide, 1 to 30 moles of sulfuric acid (preferably 3 to 10 moles), 1 to 50 moles of carboxylic acid or ester of such an acid (preferably 5 to 15 moles), and 3 to 20 moles of hydrogen peroxide (preferably 5 to 6 moles).
  • Hydrogen peroxide is advantageously used in the form of aqueous solutions, the H2O2 concentration of which can vary from approximately 35 to 75% by weight and is preferably between 65 and 75%.
  • sulfuric acid solutions containing up to 50% by weight of water.
  • liquid aliphatic acids are preferably used under the operating conditions; these acids which generally contain from 1 to 8 carbon atoms can be linear or branched, saturated or not, and contain substituents such as, for example, halogen atoms. Particularly suitable are acetic acid and propionic acid.
  • solid carboxylic acids such as heavy aliphatic acids or aromatic acids (for example benzoic acid and its substituted derivatives) by adding a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.
  • a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.
  • a carboxylic acid ester can be used.
  • This ester is preferably an aliphatic alcohol ester containing 1 to 4 carbon atoms, for example ethyl acetate, butyl acetate or ethyl propionate.
  • the oxidation according to the invention can be carried out at a temperature which can range from -20 to 140 ° C., but advantageously between 60 and 90 ° C.
  • the method according to the invention can be carried out in different ways.
  • the preferred embodiment of the invention consists in introducing hydrogen peroxide into a mixture of 2-perfluoroalkylethyl iodide, sulfuric acid and carboxylic acid or ester. This introduction is advantageously carried out with vigorous stirring with a flow rate such that the temperature of the reaction medium is itself maintained between 60 and 90 ° C.
  • the reaction is generally very rapid and takes place with a release of iodine and / or iodic acid which can be easily separated from the reaction mixture by simple filtration. Most of the iodine can thus be recovered in the form of elementary iodine by treatment of iodic acid with a conventional reducing agent such as sodium sulfite.
  • the fluorinated products can be isolated according to the usual methods, for example by decantation and washing of the organic phase with water. Finally, a product is obtained which consists mainly of the 2-perfluoroalkyl ethyl ester (R F C2H4OCOR) which can be saponified to obtain the alcohol R F CH2CH2OH or transform into another ester, in particular into acrylate or methacrylate.
  • R F C2H4OCOR 2-perfluoroalkyl ethyl ester
  • reaction mixture is then filtered to separate the iodine and the iodic acid formed, then the filtrate is decanted and the organic phase is washed three times with 50 ml of water at 25 ° C.
  • the distribution of fluorinated compounds in the organic phase thus obtained is as follows: 97.8% of R F C2H4OCOC2H5 2% of R F C2H4OH 0.2% of R F C2H4I unprocessed.
  • Example 2 is repeated, hand replacing the propionic acid with 88 g of ethyl acetate. 38 g of organic phase are then obtained, the fluorinated compounds of which are distributed as follows: 79.3% of C6F13C2H4OCOCH3 18.2% of C6F13C2H4OH 2.5% of unprocessed C6F13C2H4I.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention relates to the synthesis of 1,1,2,2-tetrahydroperfluoroalkanols and their esters by oxidizing a 2-(perfluoroalkyl)ethyl iodide using hydrogen peroxide in a carboxylic acid or carboxylic acid ester in the presence of sulphuric acid. In the process according to the invention, from 1 to 30 moles of sulphuric acid, from 1 to 50 moles of carboxylic acid or of an ester of such an acid, and from 3 to 20 moles of hydrogen peroxide per mole of 2-perfluoralkyl)ethyl iodide are used.

Description

La présente invention concerne la synthèse des tétrahydro-­1,1,2,2 perfluoroalcanols (RFCH₂CH₂OH) et de leurs esters par oxydation des iodures de perfluoroalkyl-2 éthyle correspondants (RFCH₂CH₂I) au moyen du peroxyde d'hydrogène. Le radical perfluoro­alkyle RF peut contenir de 1 à 20 atomes de carbone et être à chaîne linéaire ou ramifiée.The present invention relates to the synthesis of tetrahydro-1,1,2,2 perfluoroalkanols (R F CH₂CH₂OH) and their esters by oxidation of the corresponding 2-perfluoroalkylethyl iodides (R F CH₂CH₂I) using hydrogen peroxide. The perfluoroalkyl radical R F can contain from 1 to 20 carbon atoms and can be straight or branched chain.

Ces alcools et esters polyfluorés sont des intermédiaires intéressants pour la fabrication d'agents tensioactifs et de pro­duits hydrophobes et oléophobes. Ils peuvent en particulier être facilement transformés en esters acryliques ou méthacryliques dont la polymérisation, éventuellement avec d'autres monomères, fournit des agents d'apprêt hydrophobe et oléophobe pour les matières textiles, le cuir, le papier ou d'autres substrats. Les mélanges d'alcools et d'esters peuvent aussi être transformés entièrement en alcools.These polyfluorinated alcohols and esters are useful intermediates for the manufacture of surfactants and hydrophobic and oleophobic products. They can in particular be easily transformed into acrylic or methacrylic esters, the polymerization of which, optionally with other monomers, provides hydrophobic and oleophobic finishing agents for textiles, leather, paper or other substrates. The mixtures of alcohols and esters can also be entirely transformed into alcohols.

Plusieurs procédés de préparation de ces alcools et esters polyfluorés sont déjà connus. Le procédé décrit dans le brevet FR 1 380 579 qui consiste à faire réagir un iodure RFCH₂CH₂I avec de l'oléum puis à hydrolyser le sulfate formé, présente l'inconvénient de fournir des quantités importantes de diesters sulfuriques qui sont difficilement hydrolysables.Several processes for the preparation of these polyfluorinated alcohols and esters are already known. The process described in patent FR 1 380 579 which consists in reacting an iodide R F CH₂CH₂I with oleum and then in hydrolyzing the sulphate formed, has the drawback of providing large quantities of sulfuric diesters which are difficult to hydrolyze.

Selon un procédé décrit dans le brevet US 3 239 557 il est possible d'obtenir les esters RFCH₂CH₂OCOR par réaction d'un iodure RFCH₂CH₂I avec un sel d'acide carboxylique RCOOH. Les rendements ne sont cependant pas trés bons car il se forme des quantités plus ou moins importantes d'oléfine RFCH=CH₂.According to a process described in US Pat. No. 3,239,557, it is possible to obtain the esters R F CH₂CH₂OCOR by reaction of an iodide R F CH₂CH₂I with a carboxylic acid salt RCOOH. The yields are however not very good because more or less significant quantities of olefin R F CH = CH₂ are formed.

Les alcools RFCH₂CH₂OH peuvent aussi être obtenus selon le procédé du brevet FR 2 096 179 qui consiste à préparer les nitrates RFCH₂CH₂ONO₂ par réaction des iodures RFCH₂CH₂I avec l'acide nitri­que et à hydrogéner ces nitrates en alcool. Ce procédé présente toutefois l'inconvénient de nécessiter deux étapes réactionnelles dont la dernière doit être réalisée sous une pression élevée d'hy­drogène.The alcohols R F CH₂CH₂OH can also be obtained according to the process of patent FR 2 096 179 which consists in preparing the nitrates R F CH₂CH₂ONO₂ by reaction of the iodides R F CH₂CH₂I with nitric acid and in hydrogenating these nitrates into alcohol. However, this process has the drawback of requiring two reaction stages, the last of which must be carried out under high hydrogen pressure.

Le brevet FR 2 180 113 décrit un procédé de fabrication de mélanges d'alcools RFCH₂CH₂OH et de formiates RFCH₂CH₂OCOH par réaction à haute température des iodures RFCH₂CH₂I avec le diméthyl­formamide en présence d'un peu d'eau. Ce procédé présente l'inconvé­nient d'exiger des conditions de réaction trés sévères et de fournir comme sous-produit l'oléfine RFCH=CH₂, ce qui diminue d'autant le rendement. Une bonne sélectivité en alcool et formiate ne peut en outre être obtenue qu'en utilisant des quantités trés importantes de diméthylformamide.Patent FR 2 180 113 describes a process for manufacturing mixtures of alcohols R F CH₂CH₂OH and formates R F CH₂CH₂OCOH by reaction at high temperature of iodides R F CH₂CH₂I with dimethylformamide in the presence of a little water. This process has the drawback of requiring very severe reaction conditions and of supplying the olefin R F CH = CH₂ as a by-product, which consequently reduces the yield. In addition, good selectivity for alcohol and formate can only be obtained by using very large amounts of dimethylformamide.

Plus récemment, ou a proposé dans les brevets EP 0024224 et DE 3 035 641 de préparer ces alcools et esters polyfluorés en faisant réagir l'iodure RFCH₂CH₂I avec un peracide RCO₃H préalable­ment formé par l'addition de peroxyde d'hydrogène à un acide carbo­xylique RCO₂H en présence ou non d'une faible quantité d'acide sulfurique. Cependant, dans les conditions opératoires décrites, ce procédé conduit à une sous-production d'oléfine RFCH=CH₂ en quantité non négligeable et/ou à un faible taux de conversion de l'iodure RFCH₂CH₂I.More recently, or has proposed in patents EP 0024224 and DE 3,035,641 to prepare these polyfluorinated alcohols and esters by reacting the iodide R F CH₂CH₂I with a peracid RCO₃H previously formed by the addition of hydrogen peroxide to an acid carboxylic RCO₂H in the presence or not of a small amount of sulfuric acid. However, under the operating conditions described, this process leads to an under-production of olefin R F CH = CH₂ in a non-negligible amount and / or to a low conversion rate of iodide R F CH₂CH₂I.

Il a maintenant été trouvé un procédé permettant de pallier ces inconvénients, c'est-à-dire d'éviter une sous-production d'oléfine RFCH=CH₂ et d'obtenir néanmoins un taux de conversion trés élevé.A process has now been found which makes it possible to overcome these drawbacks, that is to say to avoid an under-production of olefin R F CH = CH₂ and nevertheless obtain a very high conversion rate.

Le procédé selon l'invention qui consiste à oxyder un iodure de perfluoroalkyl-2 éthyle au moyen du peroxyde d'hydrogène au sein d'un acide carboxylique ou d'un ester d'un tel acide et en présence d'acide sulfurique est caractérisé en ce que, pour une mole d'iodure de perfluoroalkyl-2 éthyle, on met en oeuvre de 1 à 30 moles d'acide sulfurique (de préférence,de 3 à 10 moles), de 1 à 50 moles d'acide carboxylique ou d'ester d'un tel acide (de préférence, de 5 à 15 moles), et de 3 à 20 moles de peroxyde d'hydrogène (de préférence, 5 à 6 moles).The process according to the invention which consists in oxidizing a 2-perfluoroalkylethyl iodide by means of hydrogen peroxide within a carboxylic acid or an ester of such an acid and in the presence of sulfuric acid is characterized in that, for one mole of 2-perfluoroalkylethyl iodide, 1 to 30 moles of sulfuric acid (preferably 3 to 10 moles), 1 to 50 moles of carboxylic acid or ester of such an acid (preferably 5 to 15 moles), and 3 to 20 moles of hydrogen peroxide (preferably 5 to 6 moles).

Le peroxyde d'hydrogène est avantageusement utilisé sous forme de solutions aqueuses dont la concentration en H₂O₂ peut varier d'environ 35 à 75 % en poids et est de préférence comprise entre 65 et 75 %.Hydrogen peroxide is advantageously used in the form of aqueous solutions, the H₂O₂ concentration of which can vary from approximately 35 to 75% by weight and is preferably between 65 and 75%.

Bien qu'on préfère utiliser l'acide sulfurique pur ou trés concentré (80 % en poids et plus), on peut également employer des solutions d'acide sulfurique contenant jusqu'à 50 % en poids d'eau.Although it is preferred to use pure or very concentrated sulfuric acid (80% by weight and more), it is also possible to use sulfuric acid solutions containing up to 50% by weight of water.

Comme acides carboxyliques, on utilise de préférence les acides aliphatiques liquides dans les conditions opératoires ; ces acides qui contiennent généralement de 1 à 8 atomes de carbone peuvent être linéaires ou ramifiés, saturés ou non, et contenir des substituants tels que, par exemple, des atomes d'halogène. Convien­nent particulièrement bien l'acide acétique et l'acide propionique.As carboxylic acids, liquid aliphatic acids are preferably used under the operating conditions; these acids which generally contain from 1 to 8 carbon atoms can be linear or branched, saturated or not, and contain substituents such as, for example, halogen atoms. Particularly suitable are acetic acid and propionic acid.

On peut également utiliser des acides carboxyliques solides tels que les acides aliphatiques lourds ou les acides aromatiques (par exemple l'acide benzoïque et ses dérivés substi­tués) en ajoutant un solvant tel qu'un alcool (par exemple, métha­nol, éthanol, propanol) ou un ester.It is also possible to use solid carboxylic acids such as heavy aliphatic acids or aromatic acids (for example benzoic acid and its substituted derivatives) by adding a solvent such as an alcohol (for example, methanol, ethanol, propanol) or an ester.

Comme indiqué précédemment, on peut utiliser un ester d'acide carboxylique. Cet ester est de préférence un ester d'alcool aliphatique contenant 1 à 4 atomes de carbone, par exemple l'acétate d'éthyle, l'acétate de butyle ou le propionate d'éthyle.As indicated previously, a carboxylic acid ester can be used. This ester is preferably an aliphatic alcohol ester containing 1 to 4 carbon atoms, for example ethyl acetate, butyl acetate or ethyl propionate.

L'oxydation selon l'invention peut être effectuée à une température pouvant aller de -20 à 140°C, mais avantageusement comprise entre 60 et 90°C.The oxidation according to the invention can be carried out at a temperature which can range from -20 to 140 ° C., but advantageously between 60 and 90 ° C.

Le procédé selon l'invention peut être réalisé de diffé­rentes façons. On peut par exemple opérer comme dans les brevets EP 0024224 et DE 3 035 641 en ajoutant au iodure de perfluoroalkyl-2 éthyle un mélange de peroxyde d'hydrogène, d'acide sulfurique et d'acide carboxylique ou d'ester dans les proportions requises. Il est également possible d'opérer de façon inverse en introduisant l'iodure dans un tel mélange.The method according to the invention can be carried out in different ways. One can for example operate as in patents EP 0024224 and DE 3,035,641 by adding to the perfluoroalkyl-2 ethyl iodide a mixture of hydrogen peroxide, sulfuric acid and carboxylic acid or ester in the required proportions . It is also possible to operate in reverse by introducing iodide into such a mixture.

Cependant, le mode de réalisation préféré de l'invention consiste à introduire le peroxyde d'hydrogène dans un mélange de l'iodure de perfluoroalkyl-2 éthyle, d'acide sulfurique et de l'acide ou ester carboxylique. Cette introduction est avantageuse­ment effectuée sous agitation énergique avec un débit tel que la température du milieu réactionnel se maintienne d'elle-même entre 60 et 90°C.However, the preferred embodiment of the invention consists in introducing hydrogen peroxide into a mixture of 2-perfluoroalkylethyl iodide, sulfuric acid and carboxylic acid or ester. This introduction is advantageously carried out with vigorous stirring with a flow rate such that the temperature of the reaction medium is itself maintained between 60 and 90 ° C.

La réaction est en général trés rapide et se fait avec une libération d'iode et/ou d'acide iodique qu'on peut séparer facile­ment du mélange réactionnel par simple filtration. La majeure partie de l'iode peut ainsi être récupérée sous forme d'iode élémentaire par traitement de l'acide iodique avec un réducteur classique tel que le sulfite de sodium.The reaction is generally very rapid and takes place with a release of iodine and / or iodic acid which can be easily separated from the reaction mixture by simple filtration. Most of the iodine can thus be recovered in the form of elementary iodine by treatment of iodic acid with a conventional reducing agent such as sodium sulfite.

Les produits fluorés peuvent êtres isolés suivant les méthodes habituelles, par exemple par décantation et lavage de la phase organique à l'eau. On obtient finalement un produit constitué majoritairement par l'ester de perfluoroalkyl-2 éthyle (RFC₂H₄OCOR) qu'on peut saponifier pour obtenir l'alcool RFCH₂CH₂OH ou trans­former en un autre ester, notamment en acrylate ou méthacrylate.The fluorinated products can be isolated according to the usual methods, for example by decantation and washing of the organic phase with water. Finally, a product is obtained which consists mainly of the 2-perfluoroalkyl ethyl ester (R F C₂H₄OCOR) which can be saponified to obtain the alcohol R F CH₂CH₂OH or transform into another ester, in particular into acrylate or methacrylate.

AVERTISSEMENTWARNING

Comme cela est déjà signalé dans le brevet DE 3.035.641 précité, le travail avec les peracides et le peroxyde d'hydrogène comporte d'importants risques d'inflammation et d'explosion. Il conviendra donc, lors de la mise en oeuvre du procédé selon l'inven­tion, de prendre à cet égard toutes les mesures de précaution usuelles.As already mentioned in the aforementioned patent DE 3,035,641, working with peracids and hydrogen peroxide involves significant risks of ignition and explosion. It will therefore be necessary, when implementing the method according to the invention, to take in this respect all the usual precautionary measures.

Les exemples suivants dans lesquels les pourcentages s'entendent en poids, illustrent l'invention sans la limiter.The following examples, in which the percentages are by weight, illustrate the invention without limiting it.

EXEMPLE 1EXAMPLE 1

Dans un réacteur en verre de 250 ml, muni d'un agitateur énergique, d'un réfrigérant à reflux et d'une ampoule de coulée, on charge 47,4 g (0,1 mole) d'iodure de perfluorohexyl-2 éthyle, 60 g d'acide acétique et 28 ml d'acide sulfurique à 98 %, puis on ajoute goutte à goutte en 50 minutes 24,7 g d'une solution à 70 % de peroxyde d'hydrogène (soit 0,5 mole de H₂O₂). La température s'élève d'elle-même à 75-80°C et est maintenue à cette valeur pendant encore 30 à 45 minutes aprés la fin de l'addition.47.4 g (0.1 mol) of 2-perfluorohexylethyl iodide are charged into a 250 ml glass reactor, equipped with a vigorous stirrer, a reflux condenser and a dropping funnel , 60 g of acetic acid and 28 ml of 98% sulfuric acid, then 24.7 g of a 70% solution of hydrogen peroxide (i.e. 0.5 mole of H₂O₂). The temperature rises by itself to 75-80 ° C and is maintained at this value for another 30 to 45 minutes after the end of the addition.

Le mélange réactionnel est ensuite filtré pour séparer l'iode et l'acide iodique formés, puis on décante le filtrat et on lave la phase organique trois fois avec 50 ml d'eau à 25°C.The reaction mixture is then filtered to separate the iodine and the iodic acid formed, then the filtrate is decanted and the organic phase is washed three times with 50 ml of water at 25 ° C.

On obtient ainsi 38 g de phase organique dont la réparti­tion des composés fluorés, déterminée par chromatographie, est la suivante :
95 % de C₆F₁₃C₂H₄OCOCH₃
3,1 % de C₆F₁₃C₂H₄OH
1,5 % de (C₆F₁₃C₂H₄O)₂SO₂
0,4 % de C₆F₁₃C₂H₄I non transformé.38 g of organic phase are thus obtained, the distribution of the fluorinated compounds, determined by chromatography, is as follows:
95% of C₆F₁₃C₂H₄OCOCH₃
3.1% of C₆F₁₃C₂H₄OH
1.5% of (C₆F₁₃C₂H₄O) ₂SO₂
0.4% of unprocessed C₆F₁₃C₂H₄I.

EXEMPLE 2EXAMPLE 2

Dans un réacteur identique à celui de l'exemple 1, on charge 47,4 g d'iodure de perfluorohexyl-2 éthyle, 30 ml d'acide sulfurique à 98 % et 74 g d'acide propionique, puis on ajoute goutte à goutte en 45 minutes 26,9 g d'une solution à 70 % de peroxyde d'hydrogène et on maintient ensuite pendant encore 30 minutes à 75-80°C sous agitation.In a reactor identical to that of Example 1, 47.4 g of 2-perfluorohexyl ethyl iodide, 30 ml of 98% sulfuric acid and 74 g of propionic acid are charged, then added dropwise in 45 minutes 26.9 g of a 70% solution of hydrogen peroxide and then maintained for another 30 minutes at 75-80 ° C with stirring.

Aprés filtration, décantation du filtrat et lavage au sulfite de sodium et à l'eau, on récupère 40 g de phase organique dont la répartition des composés fluorés est la suivante :
98,4 % de C₆F₁₃C₂H₄OCOC₂H₅
1,4 % de C₆F₁₃C₂H₄OH
0,2 % de C₆F₁₃C₂H₄I non transformé.After filtration, decantation of the filtrate and washing with sodium sulfite and with water, 40 g of organic phase are recovered, the distribution of the fluorinated compounds is as follows:
98.4% of C₆F₁₃C₂H₄OCOC₂H₅
1.4% of C₆F₁₃C₂H₄OH
0.2% of unprocessed C₆F₁₃C₂H₄I.

EXEMPLE 3EXAMPLE 3

En opérant comme à l'exemple 2 à partir de 37,4 g d'iodure de perfluorobutyl-2 éthyle, on obtient 28 g de phase organique dont la répartition des composés fluorés est la suivante :
97 % de C₄F₉C₂H₄OCOC₂H₅
1,5 % de C₄F₉C₂H₄OH
1,5 % de C₄F₉C₂H₄I non transformé.By operating as in Example 2 from 37.4 g of 2-perfluorobutyl ethyl iodide, 28 g of organic phase are obtained, the distribution of the fluorinated compounds being as follows:
97% of C₄F₉C₂H₄OCOC₂H₅
1.5% of C₄F₉C₂H₄OH
1.5% of unprocessed C₄F₉C₂H₄I.

EXEMPLE 4EXAMPLE 4

On opère comme à l'exemple 2, mais en remplaçant l'iodure de perfluorohexyl-2 éthyle par 53,8 g d'un mélange d'iodures RFC₂H₄I ayant la composition pondérale suivante :

Figure imgb0001
le poids moléculaire moyen de ce mélange étant voisin de 538.The procedure is as in Example 2, but replacing the 2-perfluorohexyl ethyl iodide with 53.8 g of a mixture of iodides R F C₂H₄I having the following composition by weight:
Figure imgb0001
 the average molecular weight of this mixture being close to 538.

La répartition des composés fluorés dans la phase organi­que ainsi obtenue (40 g) est la suivante :
97,8 % de RFC₂H₄OCOC₂H₅
2 % de RFC₂H₄OH
0,2 % de RFC₂H₄I non transformés.The distribution of fluorinated compounds in the organic phase thus obtained (40 g) is as follows:
97.8% of R F C₂H₄OCOC₂H₅
2% of R F C₂H₄OH
0.2% of R F C₂H₄I unprocessed.

EXEMPLE 6EXAMPLE 6

En opérant comme à l'exemple 2 à partir de 27,4 g de iodure de pentafluoro-3,3,4,4,4 butyle, on obtient 20 g de phase organique dont les composés fluorés se répartissent comme suit :
96,5 % de C₂F₅C₂H₄OCOC₂H₅
1,5 % de C₂F₅C₂H₄OH
2 % de C₂F₅C₂H₄I non transformé.By operating as in Example 2 from 27.4 g of pentafluoro-3,3,4,4,4 butyl iodide, 20 g of organic phase are obtained, the fluorinated compounds of which are distributed as follows:
96.5% of C₂F₅C₂H₄OCOC₂H₅
1.5% of C₂F₅C₂H₄OH
2% of unprocessed C₂F₅C₂H₄I.

EXEMPLE 6EXAMPLE 6

Dans un réacteur identique à celui de l'exemple 1, on charge 47,4 g d'iodure de perfluorohexyl-2 éthyle, 30 ml d'acide sulfurique à 98 % et 163 g d'acide trichloroacétique. On ajoute ensuite sous agitation 26,9 g d'une solution à 70 % de peroxyde d'hydrogène à un débit tel que la température se maintienne à 70-80°C. Quand l'addition du peroxyde d'hydrogène est terminée, on laisse sous agitation pendant encore 30 minutes.47.4 g of 2-ethyl perfluorohexyl iodide, 30 ml of 98% sulfuric acid and 163 g of trichloroacetic acid are charged into a reactor identical to that of Example 1. Then added with stirring 26.9 g of a 70% solution of hydrogen peroxide at a rate such that the temperature is maintained at 70-80 ° C. When the addition of hydrogen peroxide is complete, the mixture is left stirring for a further 30 minutes.

Aprés refroidissement à 20°C, on ajoute 100 ml d'eau. Par filtration, on récupère 12,3 g d'iode brut. Aprés décantation du filtrat et lavage de la phase organique à l'eau, on obtient 53 g d'un produit dont la répartition des composés fluorés est la suivante :
90,6 % de C₆F₁₃C₂H₄OCOCCl₃
1,1 % de C₆F₁₃C₂H₄OH
5,6 % de (C₆F₁₃C₂H₄O)₂SO₂
2,7 % de C₆F₁₃C₂H₄I non transformé.After cooling to 20 ° C, 100 ml of water are added. By filtration, 12.3 g of crude iodine are recovered. After decanting the filtrate and washing the organic phase with water, 53 g of a product are obtained, the distribution of the fluorinated compounds is as follows:
90.6% of C₆F₁₃C₂H₄OCOCCl₃
1.1% of C₆F₁₃C₂H₄OH
5.6% of (C₆F₁₃C₂H₄O) ₂SO₂
2.7% of unprocessed C₆F₁₃C₂H₄I.

EXEMPLE 7EXAMPLE 7

On opère comme à l'exemple 2, main en remplaçant les 74 g d'acide propionique par 144 g d'acide octanoïque. On obtient ainsi 56 g de phase organique dont les composés fluorés se répartissent comme suit :
98 % de C₆F₁₃C₂H₄OCOC₇H₁₅
0,8 % de C₆F₁₃C₂H₄OH
1,2 % de C₆F₁₃C₂H₄I non transformé.The procedure is as in Example 2, hand, replacing the 74 g of propionic acid with 144 g of octanoic acid. 56 g of organic phase are thus obtained, the fluorinated compounds of which are distributed as follows:
98% of C₆F₁₃C₂H₄OCOC₇H₁₅
0.8% of C₆F₁₃C₂H₄OH
1.2% of unprocessed C₁₃F₂C₂H₄I.

EXEMPLE 8EXAMPLE 8

On répète l'exemple 2, main en remplaçant l'acide propio­nique par 88 g d'acétate d'éthyle. On obtient alors 38 g de phase organique dont les composés fluorés se répartissent comme suit :
79,3 % de C₆F₁₃C₂H₄OCOCH₃
18,2 % de C₆F₁₃C₂H₄OH
2,5 % de C₆F₁₃C₂H₄I non transformé.Example 2 is repeated, hand replacing the propionic acid with 88 g of ethyl acetate. 38 g of organic phase are then obtained, the fluorinated compounds of which are distributed as follows:
79.3% of C₆F₁₃C₂H₄OCOCH₃
18.2% of C₆F₁₃C₂H₄OH
2.5% of unprocessed C₆F₁₃C₂H₄I.

Claims (7)

1. Procédé de préparation des tétrahydro-1,1,2,2 perfluoro­alcanols et de leurs esters par oxydation d'un iodure de perfluoro­alkyl-2 éthyle au moyen du peroxyde d'hydrogène au sein d'un acide carboxylique ou d'un ester d'un tel acide et en présence d'acide sulfurique, caractérisé en ce que, pour une mole d'iodure de perfluo­roalkyl-2 éthyle, on met en oeuvre de 1 à 30 moles d'acide sulfuri­que, de 1 à 50 moles d'acide carboxylique ou d'ester d'un tel acide, et de 3 à 20 moles de peroxyde d'hydrogène.1. Process for the preparation of 1,1,2,2 tetrahydro perfluoroalkanols and their esters by oxidation of a 2-perfluoroalkylethyl iodide by means of hydrogen peroxide within a carboxylic acid or an ester of such an acid and in the presence of sulfuric acid, characterized in that, for one mole of 2-perfluoroalkyl ethyl iodide, 1 to 30 moles of sulfuric acid are used, from 1 to 50 moles of carboxylic acid or ester of such an acid, and from 3 to 20 moles of hydrogen peroxide. 2. Procédé selon la revendication 1, dans lequel on met en oeuvre 3 à 10 moles d'acide sulfurique, 5 à 15 moles d'acide carboxylique ou d'ester d'un tel acide, et 5 à 6 moles de peroxyde d'hydrogène par mole d'iodure de perfluoroalkyl-2 éthyle.2. Method according to claim 1, in which 3 to 10 moles of sulfuric acid, 5 to 15 moles of carboxylic acid or of ester of such an acid, and 5 to 6 moles of peroxide are used. hydrogen per mole of 2-perfluoroalkyl ethyl iodide. 3. Procédé selon la revendication 1 ou 2, dans lequel la réaction est effectuée à une température de 60 à 90°C.3. Method according to claim 1 or 2, wherein the reaction is carried out at a temperature of 60 to 90 ° C. 4. Procédé selon l'une des revendications 1 à 3, dans lequel on introduit le peroxyde d'hydrogène dans une solution comprenant le iodure de perfluoroalkyle-2 éthyle, l'acide carboxylique ou un ester d'un tel acide, et l'acide sulfurique.4. Method according to one of claims 1 to 3, wherein the hydrogen peroxide is introduced into a solution comprising 2-perfluoroalkylethyl iodide, the carboxylic acid or an ester of such an acid, and the sulfuric acid. 5. Procédé selon l'une des revendications 1 à 4, dans lequel le peroxyde d'hydrogène est utilisé sous forme d'une solution aqueuse dont la concentration en H₂O₂ peut varier de 35 à 75 % en poids, de préférence entre 65 et 75 %.5. Method according to one of claims 1 to 4, wherein the hydrogen peroxide is used in the form of an aqueous solution whose H₂O₂ concentration can vary from 35 to 75% by weight, preferably between 65 and 75 %. 6. Procédé selon l'une des revendications 1 à 5, dans lequel on utilise l'acide sulfurique pur ou dilué avec jusqu'à 50 % en poids d'eau.6. Method according to one of claims 1 to 5, in which pure sulfuric acid or diluted with up to 50% by weight of water is used. 7. Procédé selon l'une des revendications 1 à 6, dans lequel on met en oeuvre l'acide acétique ou propionique.7. Method according to one of claims 1 to 6, in which acetic or propionic acid is used.
EP87402923A 1986-12-22 1987-12-18 Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters Expired EP0275771B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87402923T ATE45346T1 (en) 1986-12-22 1987-12-18 PRODUCTION PROCESSES OF TETRAHYDRO-1,1,2,2PERFLUOROALKANOLS AND THEIR ESTERS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8617983 1986-12-22
FR8617983 1986-12-22

Publications (2)

Publication Number Publication Date
EP0275771A1 true EP0275771A1 (en) 1988-07-27
EP0275771B1 EP0275771B1 (en) 1989-08-09

Family

ID=9342164

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87402923A Expired EP0275771B1 (en) 1986-12-22 1987-12-18 Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters

Country Status (12)

Country Link
US (1) US4791223A (en)
EP (1) EP0275771B1 (en)
JP (1) JPS63166840A (en)
KR (1) KR910000250B1 (en)
AT (1) ATE45346T1 (en)
AU (1) AU599734B2 (en)
CA (1) CA1265154A (en)
DE (1) DE3760417D1 (en)
DK (1) DK672687A (en)
ES (1) ES2010714B3 (en)
FI (1) FI875684A (en)
NO (1) NO165188C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526976A1 (en) * 1991-07-10 1993-02-10 Minnesota Mining And Manufacturing Company Perfluoroalkyl halides and derivatives
US5852148A (en) * 1991-07-10 1998-12-22 Minnesota Mining & Manufacturing Company Perfluoroalkyl halides and derivatives
US6048952A (en) * 1991-07-10 2000-04-11 3M Innovative Properties Company Perfluoroalkyl halides and derivatives

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO166122C (en) * 1986-12-22 1991-06-05 Atochem PROCEDURE FOR THE PREPARATION OF A MIXTURE OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANOLS AND THEIR ESTERS.
JP4525884B2 (en) * 1999-05-12 2010-08-18 ダイキン工業株式会社 Catalyst for producing fluorine-containing alcohol compound and method for producing fluorine-containing alcohol compound
DE102004006103A1 (en) * 2004-02-06 2005-10-20 Voith Fabrics Patent Gmbh Modular paper machine clothing
US20070244338A1 (en) * 2004-04-26 2007-10-18 Yoshio Funakoshi Method for Producing Fluorine-Containing Acrylic Ester
WO2005102982A1 (en) * 2004-04-26 2005-11-03 Daikin Industries, Ltd. Process for producing fluorinated (meth)acrylic ester
JPWO2005102984A1 (en) * 2004-04-26 2008-03-13 ダイキン工業株式会社 Method for producing fluorine-containing acrylic ester
US8212064B2 (en) * 2008-05-14 2012-07-03 E.I. Du Pont De Nemours And Company Ethylene tetrafluoroethylene intermediates
US8318877B2 (en) * 2008-05-20 2012-11-27 E.I. Du Pont De Nemours And Company Ethylene tetrafluoroethylene (meth)acrylate copolymers
EP3933963A1 (en) 2020-07-01 2022-01-05 VARTA Microbattery GmbH Method and apparatus for manufacturing electrochemical cells and electrode for an electrochemical cell

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239557A (en) * 1962-01-18 1966-03-08 Du Pont Process for converting halides to esters
EP0024224A1 (en) * 1979-08-08 1981-02-25 P C U K Produits Chimiques Ugine Kuhlmann Process for the synthesis of 1,1,2,2-tetrahydroperfluoro alcohols and their esters
DE3035641A1 (en) * 1980-09-20 1982-05-06 Hoechst Ag, 6000 Frankfurt Per:fluoro-alkyl-alkanol textile finish intermediate prepn. - by reacting per:fluoro-alkyl iodo-alkane with peroxido-carboxylic acid opt. using phase transfer catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1023768A (en) * 1972-12-21 1978-01-03 Horst Jager Polyfluoroalkyl iodides, process for their manufacture, and their use
JPS59141538A (en) * 1983-02-01 1984-08-14 Agency Of Ind Science & Technol Production of halogenated propionic acid ester
NO166122C (en) * 1986-12-22 1991-06-05 Atochem PROCEDURE FOR THE PREPARATION OF A MIXTURE OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANOLS AND THEIR ESTERS.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239557A (en) * 1962-01-18 1966-03-08 Du Pont Process for converting halides to esters
EP0024224A1 (en) * 1979-08-08 1981-02-25 P C U K Produits Chimiques Ugine Kuhlmann Process for the synthesis of 1,1,2,2-tetrahydroperfluoro alcohols and their esters
DE3035641A1 (en) * 1980-09-20 1982-05-06 Hoechst Ag, 6000 Frankfurt Per:fluoro-alkyl-alkanol textile finish intermediate prepn. - by reacting per:fluoro-alkyl iodo-alkane with peroxido-carboxylic acid opt. using phase transfer catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0526976A1 (en) * 1991-07-10 1993-02-10 Minnesota Mining And Manufacturing Company Perfluoroalkyl halides and derivatives
US5852148A (en) * 1991-07-10 1998-12-22 Minnesota Mining & Manufacturing Company Perfluoroalkyl halides and derivatives
US6048952A (en) * 1991-07-10 2000-04-11 3M Innovative Properties Company Perfluoroalkyl halides and derivatives
US6365769B1 (en) 1991-07-10 2002-04-02 3M Innovative Properties Company Perfluoroalkyl halides and derivatives

Also Published As

Publication number Publication date
AU8287487A (en) 1988-06-23
FI875684A0 (en) 1987-12-22
ATE45346T1 (en) 1989-08-15
NO165188C (en) 1991-01-09
EP0275771B1 (en) 1989-08-09
JPH0416451B2 (en) 1992-03-24
KR910000250B1 (en) 1991-01-23
DK672687D0 (en) 1987-12-21
FI875684A (en) 1988-06-23
DE3760417D1 (en) 1989-09-14
NO874942L (en) 1988-06-23
NO874942D0 (en) 1987-11-26
JPS63166840A (en) 1988-07-11
KR880007415A (en) 1988-08-27
NO165188B (en) 1990-10-01
AU599734B2 (en) 1990-07-26
DK672687A (en) 1988-06-23
ES2010714B3 (en) 1989-12-01
CA1265154A (en) 1990-01-30
US4791223A (en) 1988-12-13

Similar Documents

Publication Publication Date Title
EP0275771B1 (en) Process for the preparation of tetrahydro-1,1,2,2-perfluoroalcanols and their esters
FR2641532A1 (en) PROCESS FOR THE PREPARATION OF ACID ESTERS (BETA) -HYDROXYBUTYRIC
EP0025740B1 (en) Unsaturated fatty alcohols and process for their preparation
CA1082733A (en) Process for the preparation of derivatives of perfluoroalkane-carboxylic acids and of perfluoroalkane-sulfinic acids
EP0206899B1 (en) Process for the preparation of fluorinated alkyl(meth)acrylates
EP0276605B1 (en) Synthesis of tetrahydro-1,1,2,2-perfluoroalcanols and their esters
EP0024224B1 (en) Process for the synthesis of 1,1,2,2-tetrahydroperfluoro alcohols and their esters
CA1128542A (en) Process for preparation of esters
FR2478644A1 (en) PROCESS FOR THE PREPARATION OF MALATHION
CA2243667A1 (en) Synthesis of carboxyalkylthiosuccinic acids
EP0697401B1 (en) Synthesis of mercaptocarboxylic acid esters
EP0278822B1 (en) Process for the preparation of derivatives of perhalogenoalkanesulfinic and sulfonic acids
EP0003205A1 (en) Process for the preparation of ethylesters
FR2610924A1 (en) PROCESS FOR THE PREPARATION OF HYDROXYBIPHENYLS
EP0160577A1 (en) Process for the preparation of perfluorocarboxylic acids
CA1176650A (en) Process for preparing 1,1,2,2-tetrahydro perfluorinated alkanols and esters thereof
FR2470109A1 (en) 3-Hydroxybenzoic acid derivs. prodn. - from cresol ester by chlorination and then hydrolysis, useful as herbicide intermediates
FR2584395A1 (en) PROCESS FOR THE PREPARATION OF DECABROMODIPHENYL ETHER
BE560450A (en)
FR2575745A1 (en) Oil-soluble cobalt soaps
BE677000A (en)
FR2653129A1 (en) Process for the preparation of 7-oxocholanates
BE379406A (en)
BE428298A (en)
BE484556A (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19871223

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19890123

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 45346

Country of ref document: AT

Date of ref document: 19890815

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3760417

Country of ref document: DE

Date of ref document: 19890914

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19921019

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921204

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19921214

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19921218

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19921223

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19921231

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19930127

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19931218

Ref country code: AT

Effective date: 19931218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19931219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19931220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19931231

Ref country code: CH

Effective date: 19931231

Ref country code: BE

Effective date: 19931231

BERE Be: lapsed

Owner name: ATOCHEM

Effective date: 19931231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940701

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931218

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19941208

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19941209

Year of fee payment: 8

EUG Se: european patent has lapsed

Ref document number: 87402923.4

Effective date: 19940710

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960903

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20010301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051218